Basic indoline dyestuffs

ABSTRACT

Basic dyestuffs free of sulphonic acid groups contain an indoline group the 2-position of which is connected through a vinylene group to the N-atom of a 2,3-dihydro-4H-1,4-benzoxazine group. The dyestuffs are useful for the dyeing of leather, paper and plastics and, particularly, polyacrylonitrile or acid-modified polyester fibres.

This invention relates to basic dyestuffs free of sulphonic acid groups.

The invention provides compounds of formula I ##STR1## in which Ris--hydrogen; halogen; cyano; nitro; C₁₋₄ alkyl which is unsubstitutedor mono-substituted by phenyl, monochlorophenyl or mono (C₁₋₄alkyl)phenyl; C₁₋₄ alkoxy which is unsubstituted or mono-substituted byphenyl; phenoxy; acetyl or di-(C₁₋₄ alkyl)sulphonylamino,

R_(o) --is hydrogen, C₁₋₄ alkyl or C₁₋₄ alkoxy, or

R and R_(o) together form a group of formula --O--CH₂ --O--, --O--CH₂--CH₂ --O--, --O--CH₂ --O--CH₂ --, --CH₂)₄ or --CH₃)₃, in which theasymmetric --O--CH₂ --O--CH₂ -- group may be connected in either of bothpossible ways,

R₁ --and R₂ are independently linear C₁₋₄ alkyl,

R₃ --is allyl, unsubstituted C₁₋₄ alkyl or C₁₋₄ alkyl monosubstituted byhydroxy, phenyl, carbonamido, cyano or C₁₋₄ alkoxy,

R₄ --is hydrogen, cyano, carboxyl, C₁₋₄ alkyl, carbonamido or--COO--(C₁₋₄)alkyl,

D--is a group of formula II or III ##STR2## in which R₅ is hydrogen,C₁₋₄ alkyl, phenyl unsubstituted or substituted by one or two groupsselected from methoxy, chloro, methyl or dimethylamino, or --COO--(C₁₋₄alkyl),

R₆ and R₈ are independently hydrogen or C₁₋₄ alkyl,

R₇ is hydrogen, C₁₋₄ alkyl, phenyl or --COO--(C₁₋₄ alkyl), or

R₇ and R₅ together with the carbon atoms to which they are attached forman unsubstituted cyclopentyl or cyclohexyl ring,

R₉ is hydrogen, halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, amino, di(C₁₋₄ alkyl)amino, C₂₋₅ acylamino, --NH--SO₂ --(C₁₋₄ alkyl), --NH--SO₂ --phenyl or abenzoylamino group unsubstituted or substituted by one or two chlorineatoms or one or two C₁₋₄ alkyl groups,

X is oxygen or sulphur, and

A is an anion.

Preferred significances of the groups R-R₁₀ and X are as follows:

R: hydrogen, halogen, unsubstituted alkyl, unsubstituted orphenyl-substituted alkoxy, phenoxy or dialkylsulphonylamino

R_(o) : hydrogen

R₄ : hydrogen

R₅ : hydrogen, alkyl or phenyl

R₇ : hydrogen, alkyl or phenyl

R₉ : hydrogen, halogen, alkyl, alkoxy, amino-, di-alkylamino, acylamino,or benzoylamino; more preferably hydrogen, amino, acylamino or alkoxy.

X: oxygen.

By halogen is meant fluorine, chlorine, bromine and iodine, preferablychlorine.

Where any of R, R₁, R₂, R₆, R₇, R₈ and R₉ are alkyl, they are,independently, preferably methyl. Where R is alkoxy it is preferablymethoxy, where R is phenyl-substituted alkoxy it is preferablybenzyloxy, and where R is dialkylsulphonylamino it is preferablydimethylsulphonylamino.

Where R₃ is alkyl it is preferably methyl, ethyl or propyl, and where R₃is substituted alkyl it is preferably 2-hydroxyethyl, 2-hydroxypropyl,2-cyanoethyl or 2-carboxamidoethyl.

Where R₅ is alkyl it is preferably methyl or ethyl, more preferablymethyl.

Where R₉ is alkoxy it is preferably methoxy, and where R₉ is acylaminoit is preferably acetylamino.

Preferably R is R_(a) where R_(a) is hydrogen, chloro, methyl, methoxy,phenoxy, benzyloxy or dimethylsulphonylamino, more preferably R_(b)where R_(b) is hydrogen, chloro or methoxy.

R₃ is preferably R_(3a) where R_(3a) is methyl, ethyl, propyl, allyl,2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl or 2-carboxamidoethyl,more preferably methyl.

R₅ is preferably R_(5a) where R_(5a) is hydrogen, methyl ethyl orphenyl, more preferably R_(5b) where R_(5b) is hydrogen, methyl orphenyl.

R₆ and R₈ are preferably R_(6a) and R_(8a) where R_(6a) and R_(8a) areindependently hydrogen or methyl, more preferably hydrogen.

R₇ is preferably R_(7a) where R_(7a) is hydrogen, methyl or phenyl, morepreferably R_(7b) where R_(7b) is hydrogen or methyl.

R₉ is preferably R_(9a) where R_(9a) is hydrogen, chloro, methyl,methoxy, ethoxy, amino, acetylamino, dimethylamino or benzoylamino, morepreferably R_(9b) where R_(9b) is hydrogen, amino, acetylamino ormethoxy.

A preferred group of compounds of formula I are those of formula IV##STR3## in which R_(a) and R_(3a) are as defined above, and D₁ is agroup of formula II_(a) or III_(a) ##STR4## in which R_(5a), R_(6a),R_(7a), R_(8a) and R_(9a) are as defined above.

Particularly preferred are those of formula V ##STR5## in which R_(b),R_(5b), R_(7b) and R_(9b) are as defined above.

The invention also provides a process for the preparation of compoundsof formula I characterized by (A) the reaction of a compound of formulaVI ##STR6## with a compound of formula VII or VIII ##STR7## in thepresence of an acid of formula HA, or (B) the reaction of a compound offormula IX ##STR8## with a compound of formula X or XI ##STR9## in whichZ is =O, =N--R₁₁, or =N.sup.⊕ HR₁₁ A.sup.⊖, and R₁₁ is hydrogen

or C₁₋₄ alkyl,

in the presence of a Lewis acid.

Process variant (A) may be carried out in conventional manner, forexample in water or organic solvents or a mixture thereof at atemperature from room temperature to 80° C., preferably 50°-70° C.Preferably the acid used is hydrochloric acid. Process variant (B) isalso conventional and may be carried out in an organic solvent, forexample chlorobenzene or toluene, from room temperature to 80° C.,preferably at 50°-70° C. Preferred Lewis acids are phosphorusoxychloride and aluminium chloride.

The compounds of formulae VI and IX are known, and those of formulaeVII, VIII, X and XI are either known (for example from German Patent 2234 468) or may be prepared in analogous manner to known compounds.

The anion A.sup.⊖ in compounds of formula I may be a non-chromophoricorganic or inorganic anion, for example chloride, bromide, sulphate,bisulphate, methylsulphate, aminosulphate, perchlorate, lactate,succinate, tartrate, malate, methane sulphonate or benzoate; or may be acomplex anion for example of boric, citric, glycollic, diglycollic oradipic acids.

The anion A.sup.⊖ may be exchanged for other anions for example with theaid of an ion-exchange resin or by reaction with salts or acids. Suchreaction may take place in more than one step, for example through thehydroxide or bicarbonate, or according to French Pat. Nos. 2 028 725 or2 028 726.

The compounds of formula I are dyestuffs and are useful for the dyeingof cationically dyeable substrates such as leather, paper and plastics,and particularly for the dyeing or printing of textile substratescontaining or consisting of fibres of homopolymers or copolymers ofacrylonitrile or asymmetric dicyanoethylene, or of acid-modifiedpolyamides or polyesters. Such polyamides and polyesters are describedin Belgian Pat. No. 706 104 and U.S. Pat. No. 3 379 723 respectively.

The compounds may be worked up by conventional means into solid orliquid compositions, for example by granulation or by dissolving in asuitable solvent, optionally in the presence of additives such asstabilisers or solubilising agents such as urea. Such preparations maybe obtained for example as described in French Pat. Nos. 1 572 030 and 1581 900 or German patent publications 2 001 748 and 2 001 816.

Textile material may be dyed in neutral or acidic aqueous media attemperatures of from 60°-100° C. at atmospheric pressure or attemperatures over 100° C. under pressure. Alternatively, dyeing may becarried out in organic solvents, for example as described in Germanpatent publication No. 2 437 549.

The dyeings obtained from compounds of formula I on the above substratesshow good light fastness. The dyestuffs have good compatibility withother basic dyes, and have advantageously low compatibility numbers(K-values). The dyes have good exhaust power on the above substrates,giving dyeings with good fastness to washing, sweat, sublimation,pleating, decatising, ironing, water, seawater, dry cleaning, overdyeingand solvents. The dyestuffs are resistant to hydrolysis, have good watersolubility and give deep level dyeings.

The following Examples in which parts and percentages are by weight andtemperatures are in degrees centrigrade, illustrate the invention.

EXAMPLE 1 (Process Variant A)

23.5 Parts 1,3,3-trimethyl-5-chloro-2-methyleneindoline-ω-aldehyde and14.9 parts 3-methyl-2,3-dihydro-4H-1,4-benzoxazine are suspended in 200parts water at 50°-60°. To the stirred mixture is added dropwise over 3hr 50 parts of 2N hydrochloric acid, maintaining the temperature at50°-60°. A yellow solution is obtained, which on cooling to roomtemperature gives the dyestuff of formula ##STR10## in the form ofyellow crystals. The product may be salted out practically completely byaddition of sodium chloride. The dyestuff dyes polyacrylonitrile andbasic-dyeable polyester and polyamide fibres in brilliantgreenish-yellow tones with good light- and wet-fastness.

EXAMPLES 2-53

In manner analogous to Example 1 and using corresponding startingmaterials, dyestuffs of formula ##STR11## may be obtained, in which R,R₃, R₅, R₇, R₈ and R₉ are as shown in the following Table. The numbergiven in the column for R₉ indicates the position of the substituent.The anion A.sup.⊖ may be any of those described above.

    __________________________________________________________________________    Ex.                                                                           No.                                                                              R        R.sub.3   R.sub.5   R.sub.7                                                                             R.sub.8                                                                          R.sub.9                              __________________________________________________________________________    2  OCH.sub.3                                                                              CH.sub.3  H         H     H  H                                    3  OC.sub.2 H.sub.5                                                                       "         H         H     H  H                                        ##STR12##                                                                             "         H         H     H  H                                    5                                                                                 ##STR13##                                                                             "         H         H     H  H                                    6  Cl       "         H         H     H  H                                    7  H        n-C.sub.3 H.sub.7                                                                       C.sub.2 H.sub.5                                                                         H     H  (6) OC.sub.2 H.sub.5                 8                                                                                 ##STR14##                                                                             CH.sub.3  H         H     H  H                                    9  CH.sub.3 "         H         H     H  H                                    10 H        CH.sub.2CHCH.sub.2                                                                      H         H     H  (7) NH.sub.2                         11 NO.sub.2 CH.sub.3  H         H     H  H                                    12 H        CH.sub.2CH.sub.2 OH                                                                     H         H     H  H                                    13                                                                                ##STR15##                                                                             CH.sub.3  H         H     H  H                                    14 H                                                                                       ##STR16##                                                                              H         H     H                                                                                 ##STR17##                           15 H        CH.sub.2CH.sub.2CN                                                                      H                                                                                        ##STR18##                                                                          H  H                                    16 H        C.sub.2 H.sub.5                                                                         H         H     H  H                                    17 H        CH.sub.3  CH.sub.3  H     H  H                                    18 CN       "         "         H     H  H                                    19 H        C.sub.2 H.sub.4 CONH.sub.2                                                              H         H     H  H                                    20 COCH.sub.3                                                                             CH.sub.3  CH.sub.3  H     H  H                                    21 F        CH.sub.3  CH.sub.3  H     H  H                                    22                                                                                ##STR19##                                                                             "         "         H     H  H                                    23 H        "         "         COOC.sub.2 H.sub.5                                                                  H  H                                    24 H        "                                                                                        ##STR20##                                                                              H     H  H                                    25 H        "                                                                                        ##STR21##                                                                              H     H  H                                    26 H        "                                                                                        ##STR22##                                                                              H     H  H                                    27 H        "                                                                                        ##STR23##                                                                              H     H  H                                    28 H        "                                                                                        ##STR24##                                                                              H     H  H                                    29 H        "                                                                                        ##STR25##                                                                              H     H  H                                    30 H        "         CH.sub.3  CH.sub.3                                                                            H  H                                    31 H        "         "         "     CH.sub.3                                                                         H                                                          R.sub.5 together with R.sub.7                           32 H        "         CH.sub.2CH.sub.2CH.sub.2CH.sub.2                                                              H  H                                    33 H        "         CH.sub.3  H     H  (7) OCH.sub.3                        34 H        CH.sub.3  CH.sub.3  H     H  (7) CH.sub.3                         35 H        "         "         H     H  (7) Cl                               36 H        "         "         H     H                                                                                 ##STR26##                           37 H        "         "         H     H                                                                                 ##STR27##                           38 H        "         "         H     H                                                                                 ##STR28##                           39 H        "         "         H     H  (6) OCH.sub.3                        40 H        "         "         H     H  (6) Cl                               41 H        "         "         H     H  (6) F                                42 H        "         "         H     H  (6) CH.sub.3                         43 H        "                                                                                        ##STR29##                                                                              H     H  (6) Br                               44 H        "         CH.sub.3  CH.sub.3                                                                            H  (6) Cl                               45 H        "         "         "     H  (7) CH.sub.3                         46 H        "         "         H     H  (6) CH.sub.3                         47 H        "         "         H     H  (8) CH.sub.3                         48 H        "         "         H     H  (8) Cl                               49 H        CH.sub.3  H         H     H  H                                    __________________________________________________________________________

The dyestuffs of Examples 2-4, 22 and 33 dye polyacrylonitrile in yellowshades, those of Examples 5-9, 11-21, 23-32, 34, 35 and 39-49 ingreenish-yellow shades, and those of Examples 10 and 36-38 inreddish-yellow shades. The dyeings show good light- and wet-fastness.

EXAMPLE 54 (Process variant B)

A mixture of 14.9 parts 3-methyl-2,3-dihydro-1 H-1,4-benzoxazine, 10parts formic acid and 120 parts chlorobenzene is warmed to 140° withstirring, approx. 70 parts of solvent are removed by distillation, andthe residue is cooled to 30°.

16 Parts phosphorus oxychloride are then stirred in, and finally 17.3parts 1,3,3-trimethyl-2-methylene-2,3-dihydroindole are added dropwisewith stirring. Stirring is continued without heating for 30 min., thenfor 3 hr at 50°-60°. The dyestuff which separates from the reactionmixture is separated from the solvent, dissolved in 800 parts water andsalted out with sodium chloride, to give the dyestuff of Example 17above.

Application Example A

Polyacrylonitrile fibres are added to an aqueous dyebath at 60°containing 0.125 g/l glacial acetic acid, 0.375 g/l sodium acetate and0.15 g/l of the dyestuff of Example 1 (or a corresponding quantity of asolid or liquid preparation of this dyestuff), the liquor-to-goods ratiobeing 80:1. The dyebath is brought to the boil over 20-30 min., and keptat the boil for 90 min. The substrate is rinsed and dried to give agreenish-yellow dyeing with good fastness properties.

Application Example B

Acid-modified polyester fibres are added to an aqueous dyebath at 20°,containing 3 g/l sodium sulphate, 2 g/l ammonium sulphate and 2.5 g/l ofa nonionic carrier, the liquor-to-goods ratio being 40:1. The pH isregulated to 5.5 by addition of formic acid. The bath is heated to 60°,and 0.15 g/l of the dyestuff of Example 1 (or a corresponding amount ofa solid or liquid preparation thereof) is added. The bath is heated toboiling point over 30 minutes, and held at the boil for 60 min. Afterrinsing and drying, a greenish-yellow dyeing with good fastnessproperties is obtained.

Application Example C

Acid-modified polyester fibres are added to an aqueous dyebath at 20° C.containing 6 g/l sodium sulphate, 2 g/l ammonium sulphate and 0.15 g ofthe dyestuff of Example 1 (or a corresponding amount of a solid orliquid preparation thereof). The liquor-to-goods ratio is 30:1. The pHis regulated to 5.5 with formic acid, and the bath is heated in a closedvessel to 110°-120° over 45 minutes, and held at that temperature, withshaking, for 60 min. After rinsing and drying, a greenish-yellow dyeingwith good fastness properties is obtained.

Application Example D

Acid-modified polyamide fibres are added to an aqueous dyebath at 20°,containing 3.6 g/l sodium hydrogen sulphate, 0.7 g/l sodium sulphate, 1g/l of an auxiliary consisting of the reaction product of a phenol withexcess ethylene oxide, and 0.15 g/l of the dyestuff of Example 1 (or acorresponding amount of a solid or liquid preparation thereof). Theliquor-to-goods ratio is 80:1. The bath is heated to the boil over 30min. and kept at the boil for 60 min. After rinsing and drying agreenish-yellow dyeing with good fastness properties is obtained.

What is claimed is:
 1. A compound of formula I, ##STR30## in which R is--hydrogen; halogen; cyano; nitro; C₁₋₄ alkyl which is unsubstituted ormono-substituted by phenyl, mono-chlorophenyl or mono (C₁₋₄ alkyl)phenyl; C₁₋₄ alkoxy which is unsubstituted or mono-substituted byphenyl; phenoxy; acetyl or di-(C₁₋₄ alkyl) sulphonylamino,R_(o) --ishydrogen, C₁₋₄ alkyl or C₁₋₄ alkoxy, or, R and R_(o) together form agroup of formula --O--CH₂ --O--, --O--CH₂ --CH₂ --O--, --O--CH₂ --O--CH₂--, --CH₂)₄ or --CH₃)₃, in which the asymmetric --O--CH₂ --O--CH₂ --group may be connected in either of both possible ways, R₁ and R₂ areindependently linear C₁₋₄ alkyl, R₃ --is allyl, unsubstituted C₁₋₄ alkylor C₁₋₄ alkyl monosubstituted by hydroxy, phenyl, carbonamido, cyano orC₁₋₄ alkoxy, R₄ --is hydrogen, cyano, carboxyl, C₁₋₄ alkyl, carbonamidoor --COO--(C₁₋₄)alkyl, D--is a group of formula II or III ##STR31## inwhich R₅ is hydrogen, C₁₋₄ alkyl, phenyl unsubstituted or substituted byone or two groups selected from methoxy, chloro, methyl ordimethylamino, or --COO--(C₁₋₄ alkyl),R₆ and R₈ are independentlyhydrogen or C₁₋₄ alkyl, R₇ is hydrogen, C₁₋₄ alkyl, phenyl or--COO--(C₁₋₄ alkyl), or, R₇ and R₅ together with the carbon atoms towhich they are attached form an unsubstituted cyclopentyl or cyclohexylring, R₉ is hydrogen, halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, amino, di(C₁₋₄alkyl) amino, C₂₋₅ acylamino, --NH--SO₂ --(C₁₋₄ alkyl), --NH--SO₂--phenyl or a benzoylamino group unsubstituted or substituted by one ortwo chlorine atoms or one or two C₁₋₄ alkyl groups, X--is oxygen orsulphur, and, A--is an anion.
 2. A compound accorrding to claim 1 inwhich R is R_(a) where R_(a) is hydrogen, chloro, methyl, methoxy,phenoxy, benzyloxy or dimethylsulphonylamino.
 3. A compound according toclaim 1 in which R_(o) is hydrogen.
 4. A compound according to claim 1in which R₁ and R₂ are methyl.
 5. A compound according to claim 1 inwhich R₃ is R_(3a) where R_(3a) is methyl, ethyl, propyl, allyl,2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl or 2-carboxyamidoethyl. 6.A compound according to claim 1 in which X is oxygen.
 7. A compoundaccording to claim 6 in which D is D₁ where D₁ is a group of formula IIaor IIIa ##STR32## in which R_(5a) is hydrogen, methyl, ethyl orphenylR_(6a) and R_(8a) are independently hydrogen or methyl, R_(7a) ishydrogen, methyl or phenyl, and, R_(9a) is hydrogen, chloro, methyl,methoxy, ethoxy, amino, acetylamino, dimethylamino or benzoylamino.
 8. Acompound according to claim 7 of formula IV ##STR33## in which R_(a) ishydrogen, chloro, methyl, methoxy, phenoxy, benzyloxy ordimethylsulphonylamino, and,R_(3a) is methyl, ethyl, propyl, allyl,2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl or 2-carboxamidoethyl. 9.A compound according to claim 8 of formula V ##STR34## in which R_(b) ishydrogen, chloro or methoxy,R_(5b) is hydrogen, methyl or phenyl, R_(7b)is hydrogen or methyl R_(9b) is hydrogen, amino, acetylamino or methoxy,and and A.sup.⊖ is an anion.
 10. A compound according to claim 1whereinR is hydrogen, halogen, unsubstituted alkyl, unsubstituted orphenyl-substituted alkoxy, phenoxy or dialkylsulphonylamino; R_(o) ishydrogen; R₄ is hydrogen; R₅ is hydrogen, alkyl or phenyl; R₇ ishydrogen, alkyl or phenyl; R₉ is hydrogen, halogen, alkyl, alkoxy,amino-, dialkylamino, acylamino or benzoylamino; and X is oxygen.
 11. Acompound according to claim 1 wherein A.sup.⊖ is a non-chromophoricorganic or inorganic anion.
 12. A compound according to claim 11,wherein A.sup.⊖ is a chloride, bromide, sulphate, bisulphate,methylsulphate, aminosulphate, perchlorate, lactate, succinate,tartrate, malate, methanesulphonate or benzoate anion or a complex anionof boric, citric, glycollic, diglycollic or adipic acid.
 13. A compoundaccording to claim 9 of the formula ##STR35## wherein R₅ is hydrogen ormethyl.